EP0260799B1 - Compositions de peinture pour couche de fond - Google Patents

Compositions de peinture pour couche de fond Download PDF

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Publication number
EP0260799B1
EP0260799B1 EP87306886A EP87306886A EP0260799B1 EP 0260799 B1 EP0260799 B1 EP 0260799B1 EP 87306886 A EP87306886 A EP 87306886A EP 87306886 A EP87306886 A EP 87306886A EP 0260799 B1 EP0260799 B1 EP 0260799B1
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EP
European Patent Office
Prior art keywords
primer composition
resin
composition according
caprolactone
graft
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87306886A
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German (de)
English (en)
Other versions
EP0260799A2 (fr
EP0260799A3 (en
Inventor
Shosaku Yamamoto
Kazuo Kakinuma
Hiroshi Ishioka
Fumio Sodeyama
Junji Mayumi
Riichiro Maruta
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NOF Corp
Original Assignee
Nippon Oil and Fats Co Ltd
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Publication date
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Publication of EP0260799A2 publication Critical patent/EP0260799A2/fr
Publication of EP0260799A3 publication Critical patent/EP0260799A3/en
Application granted granted Critical
Publication of EP0260799B1 publication Critical patent/EP0260799B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/633—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polymers of compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/04—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • This invention relates to a primer composition adaptable for both steel sheet and plastic sheet as vehicle bodies.
  • the steel sheet is degreased and phosphated to form a phosphate layer thereon.
  • a chipping primer or a stoneguard coat is partially applied and then an inter coat and a top coat are formed thereon.
  • a chipping-resistant and corrosion-resistant inter coating consisting of a film forming resin composed mainly of an acidic resin having an acid value of 10 ⁇ 50, talc powder and rust-preventive pigment is applied in order to prevent the rusting and the promotion of corrosion even if the metal substrate is partially exposed by chipping, which is disclosed in Japanese Patent laid open No. 55-56,165.
  • the plastic sheet is degreased, dried and coated with an exclusive primer for the plastic sheet. Then, an exclusive inter coat and an exclusive top coat are successively formed thereon. In this case, the formation of the exclusive inter coat may be omitted.
  • Japanese Patent Application Publication No. 51-36,285 discloses a primer composed of a reaction product between ungelled hydroxy-containing urethane reactant and polycarboxylic acid or its anhydride and an aminoplast resin for polyurethane resin used as a sheet material in automobile bumper or molded article.
  • Japanese Patent laid open No. 59-30,830 discloses a primer consisting mainly of chlorinated polypropylene for polypropylene resin used as a sheet material in the automobile bumper.
  • a primer composition for plastic parts comprising a resin obtained by grafting propylene-ethylene copolymer with maleic acid or maleic anhydride and a conductive substance is used as disclosed in Japanese Patent laid open No. 61-76,557.
  • the painted plastic sheet is assembled onto the painted steel sheet, which is transferred to subsequent step.
  • the plastic sheet is degreased, dried, coated with the above exclusive primer, baked and then assembled onto the steel sheet previously degreased, phosphated and coated with an under coat, and thereafter the common inter coat and top coat are formed and baked on the assembly of the plastic sheet and steel sheet.
  • a primer composition consisting mainly of a polycaprolactone graft polymer having a primary hydroxyl group, which is obtained by graft-polymerizing a styrene-butadiene-styrene block copolymer or its hydrogenated polymer (component A) with a ring-opened polymer of ⁇ -caprolactone (component B), is applied onto the under coat formed by electrodeposition in case of the steel sheet and as a primer for plastic in case of the plastic sheet, whereby the simultaneous painting for inter coat and top coat as a hard coating used for steel sheet is possible and the aforementioned problems can be solved, and as a result the invention has been accomplished.
  • a polycaprolactone graft polymer having a primary hydroxyl group which is obtained by graft-polymerizing a styrene-butadiene-styrene block copolymer or its hydrogenated polymer (component A) with a ring-opened polymer of ⁇ -
  • the invention provides a primer composition consisting mainly of a polycaprolactone graft polymer having a primary hydroxyl group, which is obtained by graft-polymerizing a styrene-butadiene-styrene block copolymer or its hydrogenated polymer (component A) with a ring-opened polymer of ⁇ -caprolactone (component B) and has a grafting ratio of the ring-opened polymer of ⁇ -caprolactone within a range of 0.5 ⁇ 50% by weight.
  • the polycaprolactone graft polymer as a main component in the primer composition according to the invention is obtained by graft polymerization of the component A with the component B as mentioned later.
  • the production method of styrene-butadiene-styrene block copolymer used in the formation of the resin of component A according to the invention is well-known in the art, a typical example of which is disclosed in U.S. -A- 3,265,765.
  • this method includes solution polymerization of a mixture of aromatic monovinyl hydrocarbon monomer and conjugated diene monomer in the presence of a catalyst having the general formula of R(Li)x, wherein x is an integer of 1 ⁇ 4 and R is a hydrocarbon residue selected from aliphatic, alicyclic and aromatic residues.
  • intermolecular double bonds of the styrene-butadiene-styrene block copolymer may be subjected to hydrogenation.
  • the production of such a hydrogenated polymer is disclosed, for example, in Japanese Patent Application Publication No. 42-8,704, No. 43-6,636, No. 45-20,504, No. 48-3,555.
  • ⁇ -caprolactone is subjected to ring opening polymerization with a low molecular weight hydroxyl group-containing acrylic or methacrylic ester (hereinafter referred to as hydroxyl group-containing monomer) to form ⁇ , ⁇ -unsaturated group containing polycaprolactone (hereinafter referred to as PCL monomer), which is directly subjected to graft polymerization to form a polycaprolactone graft polymer.
  • hydroxyl group-containing monomer a low molecular weight hydroxyl group-containing acrylic or methacrylic ester
  • PCL monomer polycaprolactone
  • a hydroxyl group-containing monomer is graft-polymerized at a first stage and then subjected to ring opening polymerization with ⁇ -caprolactone at a second stage to form a polycaprolactone graft polymer.
  • a polycaprolactone graft polymer is obtained by simultaneously performing the first stage graft polymerization of the hydroxyl group-containing polymer and the second stage ring opening polymerization of ⁇ -caprolactone as described in the above second method.
  • hydroxyalkyl esters of acrylic or methacrylic acid such as 2-hydroxymethyl ester of acrylic or methacrylic acid, 2-hydroxyethyl ester of acrylic or methacrylic acid, 2-hydroxypropyl ester of acrylic or methacrylic acid, 2-hydroxybutyl ester of acrylic or methacrylic acid.
  • the PCL monomer is ⁇ , ⁇ -unsaturated group containing monomer obtained by subjecting the above hydroxyl group-containing monomer to ring opening polymerization with ⁇ -caprolactone.
  • graft polymerization of the PCL monomer or hydroxyl group-containing monomer with styrene-butadiene-styrene block copolymer or its hydrogenated polymer there are a method wherein radical polymerization is performed by melting and kneading the mixture through an extruder, a method wherein the block copolymer is dispersed in an aromatic hydrocarbon solvent such as toluene, xylene, benzene or the like containing a radical polymerization initiator and added with PCL monomer or hydroxyl group-containing monomer and then heated to perform radical polymerization.
  • an aromatic hydrocarbon solvent such as toluene, xylene, benzene or the like containing a radical polymerization initiator
  • radical polymerization initiator use may be made of any radical initiators usually used, a typical example of which includes organic peroxides and azonitriles.
  • organic peroxide mention may be made of alkyl peroxide, aryl peroxide, acyl peroxide, aroyl peroxide, ketone peroxide, peroxy carbonate and peroxy carboxylate.
  • the alkyl peroxide includes diisopropyl peroxide, di-ter-butyl peroxide and tert-butyl hydroperoxide.
  • the aryl peroxide includes dicumyl peroxide and cumyl hydroperoxide.
  • the acyl peroxide includes dilauroyl peroxide.
  • the aroyl peroxide includes dibenzoyl peroxide.
  • the ketone peroxide includes methylethylketone peroxide and cyclohexanone peroxide.
  • ⁇ -caprolactone and a catalyst for ring opening polymerization such as tetrabutyl titanate or dibutyltin dilaurate are supplied to a hydroxyl group-containing resin solution and then the reaction system is maintained at a temperature of 140 ⁇ 150°C to polymerize ⁇ -caprolactone to the hydroxyl group of the resin through ring opening.
  • the grafting ratio of component B being the ring opened polymer of ⁇ -caprolactone is 0.5 ⁇ 50% by weight.
  • the grafting ratio is less than 0.5% by weight, the grafting effect through ring opening of ⁇ -caprolactone is insufficient, and the impact resistance at low temperature (-30°) for plastic sheet as well as the chipping resistance of steel sheet are poor, while when it exceeds 50% by weight, the adhesion property for steel and plastic sheets is low and the humidity resistance is poor.
  • a ratio of component B/components A+B is within a range of 0.005 ⁇ 0.5.
  • the primer composition according to the invention may contain not more than 30% by weight as solid content of the other resin and crosslinking agent in addition to the polycaprolactone graft polymer composed of components A and B. When the amount of these additives exceeds 30% by weight, the impact resistance at low temperature and the chipping resistance lower.
  • the other resin mention may be made of acrylic resin, polyester resin, epoxy resin, alkyd resin, chlorinated and/or maleated polyolefin resin.
  • the crosslinking agent includes (1) self-reaction type compounds and (2) polyisocyanate compounds.
  • the self-reaction type compound (1) mention may be made of amino resins such as melamine resin and urea resin modified with an alcohol such as methanol, ethanol, n-butanol, isobutanol; and acrylic resins obtained by copolymerizing a polymerizable unsaturated group containing compound (e.g.
  • polyfunctional acrylates such as trimethylolpropane triacrylate, polyethylene glycol diacrylate, penthaerythritol triacrylate; epoxy compounds esterified with acrylic or methacrylic acid; polyurethane acrylate or methacrylate obtained by reacting a polyisocyanate compound as mentioned below with acrylic or methacrylic acid; melamine acrylate or methacrylate obtained by reacting the above mentioned melamine resin with acrylic or methacrylic acid) with an acryl monomer having a functional group such as carboxyl group, hydroxyl group, amino group or methylol group.
  • polyisocyanate compound (2) mention may be made of aromatic and aliphatic diisocyanates such as tolylene diisocyanate, 4,4 ⁇ -diphenylmethane diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate; addition products of the aromatic and aliphatic diisocyanate with diol or triol; polyisocyanates such as chain trimers bonded through biuret reaction and cyclic trimers; and blocked isocyanate compounds obtained by hindering a whole or a part of isocyanate groups contained in the aforementioned polyisocyanate compound with a blocking agent such as lower alcohol, ⁇ -caprolactone, methylethylketoxime, diethyl malonate or phenol.
  • aromatic and aliphatic diisocyanates such as tolylene diisocyanate, 4,4 ⁇ -diphenylmethane diisocyanate
  • crosslinking agents are used alone or in admixture.
  • the crosslinking agent may be used together with a resin having an active hydrogen-containing functional group such as carboxyl group, hydroxyl group, amino group or imino group, e.g. acrylic resin, polyester resin and polyurethane resin, or an epoxy compound having at least one epoxy group, preferably two or more epoxy groups in the molecule.
  • a resin having an active hydrogen-containing functional group such as carboxyl group, hydroxyl group, amino group or imino group, e.g. acrylic resin, polyester resin and polyurethane resin, or an epoxy compound having at least one epoxy group, preferably two or more epoxy groups in the molecule.
  • the primer composition according to the invention may contain a pigment.
  • a pigment mention may be made of inorganic and organic pigments usually used in the paint, such as titanium dioxide, carbon black, talc, kaolin, calcium carbonate, magnesium carbonate, barium sulfate, iron oxide, cyanine blue and quinacridone red.
  • inorganic and organic pigments usually used in the paint such as titanium dioxide, carbon black, talc, kaolin, calcium carbonate, magnesium carbonate, barium sulfate, iron oxide, cyanine blue and quinacridone red.
  • a conductive pigment particularly conductive carbon black can be used, wherein the surface resistivity is usually suitable to be not more than 1010 ⁇ cm.
  • a ratio of pigment to solid resin content is 0 ⁇ 2.0.
  • this ratio exceeds 2.0, the flexibility of the coating is poor, and the chipping resistance on the steel sheet and the chipping resistance and impact resistance on the plastic sheet are poor.
  • the usable organic solvent is enough to uniformly dissolve the resins and stably store them for a long-time period, and includes organic solvents for usual paint, e.g. aliphatic hydrocarbon solvents such as mineral spirit and n-hexane; aromatic hydrocarbon solvents such as toluene and xylene; ester series solvents such as ethyl acetate and butyl acetate; ketone series solvents such as methyl ethyl ketone and methyl isobutyl ketone.
  • organic solvents for usual paint e.g. aliphatic hydrocarbon solvents such as mineral spirit and n-hexane
  • aromatic hydrocarbon solvents such as toluene and xylene
  • ester series solvents such as ethyl acetate and butyl acetate
  • ketone series solvents such as methyl ethyl ketone and methyl isobutyl ketone.
  • the primer composition comprises 50 ⁇ 98% by weight of the organic solvent.
  • the primer composition according to the invention may be compounded with additives for paint such as surface regulating agent, antisettle agent, heat degradation preventing agent, light degradation preventing agent and pigment dispersing agent as well as a reaction catalyst promoting the reaction.
  • additives for paint such as surface regulating agent, antisettle agent, heat degradation preventing agent, light degradation preventing agent and pigment dispersing agent as well as a reaction catalyst promoting the reaction.
  • the primer composition according to the invention may be produced by the usual paint manufacturing process or pigment dispersing process.
  • the primer composition does not contain a pigment, it can be produced by mixing the resins with, if necessary, additives for paint and organic solvent in the well-known agitating device such as dissolver to form a uniform resin solution.
  • the primer composition contains a pigment, it can be produced by dispersing the pigment into a part or whole of the resin in the well-known pigment dispersing machine such as attritor and sand mill and then adding the remaining resin, organic solvent and additives for paint thereto so as to adjust the viscosity to a given value.
  • primer composition As a means for applying the primer composition according to the invention, use may be made of well-known painting manners such as air spraying, electrostatic air spraying and electrostatic spray painting.
  • the primer composition according to the invention is simultaneously applicable to the steel sheet for vehicle body after the painting of under coat and the plastic sheet after the degreasing and drying. After the application of the primer composition, the primer coating is left to stand at room temperature for 1 ⁇ 10 minutes, or the forced drying is carried out at 80°C for about 30 minutes. Then, inter coat and top coat usually used can be formed thereon.
  • inter coat Even when the primer composition is applied to both the steel sheet and plastic sheet, the painting of inter coat can be omitted, if necessary.
  • a paint for inter coat and top coat there may be used paints usually used in the steel sheet for vehicle body and the plastic sheet.
  • plastic material applicable to the primer composition according to the invention mention may be made of ones used as a plastic for vehicle body, such as polyamide resin, polybutylene terephthalate resin, polyurethane resin, polycarbonate resin, unsaturated polyester resin, polyphenylene oxide resin, polypropylene resin, a mixture thereof and a reinforced resin thereof.
  • primer composition according to the invention has been described with respect to the painting of the vehicle body, it is a matter of course that such a primer composition is applicable to simultaneous painting on a combination of steel sheet and plastic sheet as another product or a single painting on the steel sheet and plastic sheet.
  • the primer composition according to the invention can simultaneously be applied to the steel sheet for vehicle body and the plastic sheet for vehicle body owing to the presence of the polycaprolactone graft polymer composed of the components A and B at a particular weight ratio as a main component so that it is possible to simultaneously conduct the painting of the same hard inter coat and hard top coat to both the sheets in the same painting equipment and to effect the baking in the same baking furnace. Therefore, the uniformity of qualities in the painted coats on both the sheets, for example, appearance qualities such as color tone, gloss and the like and durability qualities such as weather resistance and chemical resistance can be made complete.
  • the chipping resistance, adhesion property, humidity resistance, heating-cooling cycle property and gasoline resistance are improved, while when it is applied to various plastic sheets for vehicle body, the chipping resistance, adhesion property, humidity resistance, heating-cooling cycle property, gasoline resistance and impact resistance are improved.
  • the precipitates were dried under a reduced pressure while temperature rising to obtain a white powdery polycaprolactone graft polymer having a solid content of 100%.
  • the ring-opened polymer of ⁇ -caprolactone was grafted in an amount of 1.7%.
  • the resulting polycaprolactone graft polymer was dissolved in a mixed solvent of xylene and methyl ethyl ketone with a mixing ratio of 90:10 by warming to obtain a resin varnish I having a solid content of 20%.
  • Kraton G-1650® (trade name, made by Shell Chemical Corp., solid content: 100%) was added 100 g of 2-hydroxyethyl ester of methacrylic acid, and then the graft polymerization was effected in the same manner as in the resin varnish I to obtain a powdery graft resin of 2-hydroxyethyl ester of methacrylic acid having a grafting ratio of 3.4% by weight.
  • the resulting resin was dissolved in xylene by warming to obtain a 20% resin solution.
  • 1,000 g of the resulting resin solution was charged into a flask of 2l capacity and heated to 145°C, to which were added 86 g of ⁇ -caprolactone and 1 g of a 10% solution of tetrabutyl titanate in xylene.
  • the resulting mixture was reacted at 145°C for 24 hours to obtain a solution of polycaprolactone graft polymer.
  • the grafting ratio of the ring-opened polymer of ⁇ -caprolactone was 30.2%.
  • reaction product was cooled to about room temperature and added with a proper amount of a mixed solvent of xylene and methyl ethyl ketone with a mixing ratio of 90:10 to obtain a resin varnish II having a solid content of 20%.
  • the reaction product was cooled to about room temperature and added with acetone to form precipitates, which were filtered, repeatedly washed with acetone and dried under a reduced pressure while temperature rising to obtain a white powder of polycaprolactone graft polymer having a solid content of 100%.
  • the grafting ratio of the ring-opened polymer of ⁇ -caprolactone was 9.6%.
  • the resulting polymer was dissolved in a mixed solvent of xylene and methyl ethyl ketone with a mixing ratio of 90:10 to obtain a resin varnish III having a solid content of 20%.
  • the resin varnish was diluted with toluene so as to adjust a spraying viscosity to 12 seconds (20°C) as Ford cup No. 4.
  • Coronate DC-2725® (trade name, made by Nippon Polyurethane Industry Co., Ltd., solid content: 80%)
  • Yuban 22R-60® (trade name, made by Mitsui Toatsu Chemicals, Inc., solid content: 60%)
  • Yunistol P-401® (trade name, made by Mitsui Toatsu Chemicals, Inc., solid content: 8%)
  • Acrylic 49-394-lM® (trade name, made by Dainippon Ink and Chemicals, Inc., solid content: 50%)
  • Titanium dioxide
  • Talc LMR-100® (trade name, made by Fuji Talc K.K.)
  • a cold rolled steel sheet of 0.8 mm ⁇ 70 mm ⁇ 150 mm was subjected to a phosphating treatment with Bonderite #3004® (trade name, made by Nippon Parkerizing Co., Ltd.), coated with a cation electropaint of Power Top U-100® (trade name, made by Nippon Paint Co., Ltd.) as an under coat and then dried by baking at 175°C for 20 minutes.
  • the dried thickness of the resulting electrocoating was 20 ⁇ m.
  • each of the aforementioned primer compositions was applied by an air spray painting process, and thereafter Epico No. 1500 Sealer TM-2® (trade name, made by Nippon Oil and Fats Co., Ltd.) was applied as an amino/oil-free polyester resin series inter coat of wet-on-wet system by an air spray painting process and dried by baking at 140°C for 30 minutes.
  • the dried thickness of the primer was 5 ⁇ 8 ⁇ m, and that of the inter coat was 30 ⁇ 35 ⁇ m.
  • an amino/alkyd resin series solid color of Melami No. 1500 White® (trade name, made by Nippon Oil and Fats Co., Ltd.) was applied as a top coat by an air spray painting process and dried by baking at 140°C for 30 minutes.
  • the dried thickness of the top coat was 40 ⁇ m.
  • a plastic sheet having a size of 3 mm ⁇ 70 mm ⁇ 150 mm was degreased with a vapor of 1,1,1-trichloroethane (74°C) for 60 seconds in case of the sheets A ⁇ D and F ⁇ G and with isopropyl alcohol for 60 seconds in case of the sheet E, dried, coated with the aforementioned primer by an air spray painting process, and then coated with Epico No. 1500 Sealer TM-2 as an amino/oil free polyester resin series inter coat of wet-on-wet system by an air spray painting process, which was then dried by baking at 140°C for 30 minutes.
  • the dried thickness of the primer was 5 ⁇ 8 ⁇ m, and that of the inter coat was 30 ⁇ 35 ⁇ m.
  • the amino/alkyd resin paint of Melami No. 1500 White was applied as a top coat by an air spray painting process and dried by baking at 140°C for 30 minutes.
  • the dried thickness of the top coat was 40 ⁇ m.
  • Example 2 The same procedure as described in Example 1 was repeated except that the application of the primer composition was omitted.
  • Rust number of less than 20 ⁇ (excellent) Rust number of not less than 20 but less than 50, ⁇ (acceptable) Rust number of not less than 50, ⁇ (bad)
  • the evaluation standard was ⁇ (no blistering, excellent), ⁇ (presence of blister having a diameter of less than 0.2 mm, acceptable) and ⁇ (presence of blister having a diameter of not less than 0.2 mm, unacceptable).
  • test sheet was immersed in gasoline for 1 hour to evaluate color change, swelling and peeling of the coating.
  • evaluation standard was ⁇ (no change; excellent), ⁇ (slightly change; acceptable) and ⁇ (considerably change; bad).
  • a value of impact energy when a point of impact shot through the test sheet was measured by means of a high-speed impact testing machine made by Rheometric Corporation under such conditions that a tip diameter of impact point was 1.6 cm (5/8 inch), a holder was 5.1 cm (2 inch) and an impact speed was 11.1 m/sec., from which a yield energy value (joule) at -40°C was calculated.
  • the use of the primer composition according to the invention is excellent in the chipping resistance, adhesion property, humidity resistance and gasoline resistance for the steel sheet and excellent in the chipping resistance, adhesion property, humidity resistance, gasoline resistance and impact resistance at low temperature for all plastic sheets, so that it can ensure the good balance of total film performances required as a paint for automobiles.
  • Comparative Example 1 is poor in the chipping resistance for the steel sheet and in the impact resistance at low temperature for all plastic sheets because the grafting ratio of ⁇ -caprolactone ring-opened polymer is less than 0.5%.
  • Comparative Example 2 though the resin composition is the same as in Example 1, the ratio P/B exceeds 2.0 due to the excess addition of pigment, so that the chipping resistance and humidity resistance are poor for the steel sheet, and the chipping resistance, impact resistance at low temperature and humidity resistance are poor for all plastic sheets.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Paints Or Removers (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Graft Or Block Polymers (AREA)

Claims (9)

  1. Composition pour couche de fond comprenant un polymère greffé de polycaprolactone ayant des groupes hydroxyle primaires, qui peut être obtenu par polymérisation par greffage d'un copolymère séquencé styrène-butadiène-styrène facultativement hydrogéné (composant A) avec un poly-ε-caprolactone (composant B), pouvant être obtenu par polymérisation par ouverture de cycle de ε-caprolactone sur le groupe hydroxyle d'un monomère insaturé, et qui a un taux de greffage B/(A+B) compris entre 0,5 et 50% en poids.
  2. Composition pour couche de fond selon la revendication 1, dans laquelle le polymère greffé de polycaprolactone peut être obtenu en polymérisant par greffage le composant (A) avec un polycaprolactone contenant un groupe insaturé en α, β.
  3. Composition pour couche de fond selon la revendication 1, dans laquelle le polymère greffé de polycaprolactone peut être obtenu en polymérisant par greffage le composant A avec un ester acrylique ou méthacrylique contenant des groupes hydroxyle et en polymérisant ensuite ε-caprolactone par une réaction d'ouverture de cycle sur ces groupes hydroxyle.
  4. Composition pour couche de fond selon la revendication 1, dans laquelle le polymère greffé de polycaprolactone peut être obtenu en effectuant simultanément une polymérisation par greffage du composant A avec un ester acrylique ou méthacrylique contenant des groupes hydroxyle et une polymérisation par ouverture de cycle de ε-caprolactone.
  5. Composition pour couche de fond selon la revendication 1, contenant jusqu'à 30% en poids comme teneur en solides dans le total d'une autre résine et d'un agent de réticulation.
  6. Composition pour couche de fond selon la revendication 5, dans laquelle cette résine est choisie parmi une résine acrylique, des résines polyesters, des résines époxy, des résines alkyds et des résines polyoléfines chlorées et/ou maléinées.
  7. Composition pour couche de fond selon la revendication 5, dans laquelle l'agent de réticulation est choisi parmi des résines aminées modifiées, des composés contenant des groupes insaturés polymérisables, des résines acryliques, des composés polyisocyanates et des composés isocyanates bloqués.
  8. Composition pour couche de fond selon la revendication 1, contenant un pigment avec un rapport du pigment à la teneur en polymères pouvant atteindre 2,0.
  9. Composition pour couche de fond selon la revendication 1, contenant 50 à 98% en poids d'un solvant organique.
EP87306886A 1986-08-21 1987-08-04 Compositions de peinture pour couche de fond Expired - Lifetime EP0260799B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP61194076A JPH0710957B2 (ja) 1986-08-21 1986-08-21 塗装用プライマー組成物
JP194076/86 1986-08-21

Publications (3)

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EP0260799A2 EP0260799A2 (fr) 1988-03-23
EP0260799A3 EP0260799A3 (en) 1990-01-10
EP0260799B1 true EP0260799B1 (fr) 1993-04-07

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EP87306886A Expired - Lifetime EP0260799B1 (fr) 1986-08-21 1987-08-04 Compositions de peinture pour couche de fond

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US (1) US4874818A (fr)
EP (1) EP0260799B1 (fr)
JP (1) JPH0710957B2 (fr)
DE (1) DE3785281D1 (fr)

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CN107810217B (zh) * 2015-06-30 2020-11-20 陶氏环球技术有限责任公司 粘合促进剂和用于在极性织物上使用以粘结非极性基材的方法
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EP3583144B1 (fr) * 2017-02-17 2020-10-28 3M Innovative Properties Company Copolymères triblocs
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US11466115B2 (en) 2018-06-01 2022-10-11 3M Innovative Properties Company Porous membranes including triblock copolymers
CN110713778B (zh) * 2019-11-08 2021-06-11 上海昱彩包装材料有限公司 一种高储存稳定性高光印铁涂料
EP4144911A4 (fr) 2020-04-30 2023-10-11 Bridgestone Corporation Composition adhésive pour câbles à fibre organique, corps composite de câble à fibre organique- caoutchouc et pneumatique
EP4219190A4 (fr) 2020-09-23 2024-03-27 Bridgestone Corporation Composition adhésive pour liaison caoutchouc/résine, composite organique-fibre-cordon/caoutchouc, et pneu
EP4265699A4 (fr) 2020-12-15 2024-06-19 Bridgestone Corporation Composition adhésive, composite caoutchouc-câblé de fibres organiques et pneu
WO2022137861A1 (fr) 2020-12-23 2022-06-30 株式会社ブリヂストン Composition adhésive, et matériau de résine, article en caoutchouc, composite fibre-caoutchouc organique et pneu l'utilisant
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Also Published As

Publication number Publication date
US4874818A (en) 1989-10-17
EP0260799A2 (fr) 1988-03-23
EP0260799A3 (en) 1990-01-10
JPH0710957B2 (ja) 1995-02-08
DE3785281D1 (de) 1993-05-13
JPS6351474A (ja) 1988-03-04

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